Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052300/at2442sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052300/at2442Isup2.hkl |
CCDC reference: 667451
A mixture of 6-bromo-2-hydroxynaphthalein (2.23 g, 0.01 mol) and ethyl chloroacetate(1.3 ml, 0.01 mol) was refluxed in acetone (50 ml) with anhydrous K2CO3 (2.76 g, 0.02 mol) for 5 h on a water bath. The reaction mixture was cooled to room temperature and filtered to remove the K2CO3 and the filtrate was concentrated over water bath to obtain the title compound. It was then recrystallized using acetonitrile [m.p.:335–338 K]. Analysis for C14H13BrO3: Found(Calculated): C 54.31 (54.39), H 4.19% (4.24%).
All H atoms were found in a difference map, but geometrically positioned and refined with fixed individual displacement parameters [U(H) = 1.2 Ueq(C) or U(H) = 1.5 Ueq(Cmethyl)] using a riding model with C—H ranging from 0.95 Å to 0.99 Å.
The title compound is an intermediate in the preparation of naproxen, a non-steroidal anti-inflammatory drug (NSAID) commonly used for the reduction of high to extreme pain, fever, inflammation and stiffness caused by conditions such as osteoarthritis, rheumatoid arthritis, psoriatic arthritis, gout, ankylosing spondylitis, injury. Naproxen is a member of the 2-arylpropionic acid (profen) family of NSAIDs. The structures the related compounds viz., naproxen (Ravikumar et al., 1985), 6-methoxy-2-naphthyl acetic acid ester-glycolamide (Sharma et al., 2004), 1-(5-chloro-6-methoxynaphthalen-2-yl)propan-1-one (Ye et al., 2006), complex of a lisuride derivative and (S)-naproxen (Bachechi et al., 1997), absolute configuration of (R)-1-phenylethylammonium (S)-2-(6-methoxy-2-naphthyl)propionate (Dupont et al., 1996), N'-isopropylidene-6-methoxy-2-naphthohydrazide (Sarojini et al., 2007), ethyl 6-methoxy-2-naphthoate (Yathirajan et al., 2007) have been published. A new derivative was prepared and its crystal structure is reported.
Geometric parameters of the title compound are in the usual ranges. Neglecting the H atoms, the molecule comprises two planar halves, the bromonaphthyl moiety [r.m.s. deviation 0.010 Å] and the ethoxycarbonylmethoxy moiety [r.m.s. deviation 0.018 Å]. The dihedral angle between these moieties is 79.23 (7)°. The crystal packing is stabilized by a weak C—H···O hydrogen bond.
For related literature, see: Bachechi et al. (1997); Dupont et al. (1996); Ravikumar et al. (1985); Sarojini et al. (2007); Sharma et al. (2004); Yathirajan et al. (2007); Ye et al. (2006).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level. | |
Fig. 2. The formation of the title compound. |
C14H13BrO3 | F(000) = 624 |
Mr = 309.15 | Dx = 1.582 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9086 reflections |
a = 4.9979 (5) Å | θ = 2.7–25.7° |
b = 9.3847 (7) Å | µ = 3.16 mm−1 |
c = 27.778 (3) Å | T = 173 K |
β = 94.857 (8)° | Block, colourless |
V = 1298.2 (2) Å3 | 0.31 × 0.25 × 0.23 mm |
Z = 4 |
Stoe IPDSII two-circle diffractometer | 2376 independent reflections |
Radiation source: fine-focus sealed tube | 2076 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
ω scans | θmax = 25.4°, θmin = 2.6° |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −6→6 |
Tmin = 0.441, Tmax = 0.530 | k = −11→10 |
9302 measured reflections | l = −33→29 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0623P)2 + 0.6519P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2376 reflections | Δρmax = 0.58 e Å−3 |
164 parameters | Δρmin = −0.86 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0201 (18) |
C14H13BrO3 | V = 1298.2 (2) Å3 |
Mr = 309.15 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.9979 (5) Å | µ = 3.16 mm−1 |
b = 9.3847 (7) Å | T = 173 K |
c = 27.778 (3) Å | 0.31 × 0.25 × 0.23 mm |
β = 94.857 (8)° |
Stoe IPDSII two-circle diffractometer | 2376 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 2076 reflections with I > 2σ(I) |
Tmin = 0.441, Tmax = 0.530 | Rint = 0.063 |
9302 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.58 e Å−3 |
2376 reflections | Δρmin = −0.86 e Å−3 |
164 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.71291 (7) | 0.13541 (4) | 0.159251 (11) | 0.04132 (18) | |
O1 | 0.3202 (4) | 0.2554 (2) | 0.43981 (7) | 0.0302 (5) | |
O2 | 0.5705 (4) | 0.5159 (2) | 0.43859 (8) | 0.0329 (5) | |
O3 | 0.1838 (4) | 0.62828 (18) | 0.44924 (8) | 0.0245 (4) | |
C1 | 0.1656 (6) | 0.3806 (3) | 0.44683 (11) | 0.0258 (6) | |
H1A | 0.0923 | 0.3760 | 0.4788 | 0.031* | |
H1B | 0.0125 | 0.3849 | 0.4218 | 0.031* | |
C2 | 0.3349 (5) | 0.5135 (3) | 0.44403 (9) | 0.0212 (6) | |
C3 | 0.3183 (6) | 0.7654 (3) | 0.44642 (12) | 0.0318 (7) | |
H3A | 0.3878 | 0.7775 | 0.4143 | 0.038* | |
H3B | 0.4708 | 0.7719 | 0.4715 | 0.038* | |
C4 | 0.1136 (8) | 0.8775 (3) | 0.45435 (16) | 0.0451 (9) | |
H4A | 0.1958 | 0.9720 | 0.4525 | 0.068* | |
H4B | 0.0475 | 0.8646 | 0.4863 | 0.068* | |
H4C | −0.0365 | 0.8694 | 0.4294 | 0.068* | |
C11 | 0.3974 (5) | 0.2311 (3) | 0.39419 (10) | 0.0242 (6) | |
C12 | 0.6027 (6) | 0.1268 (3) | 0.39287 (12) | 0.0294 (6) | |
H12 | 0.6735 | 0.0822 | 0.4219 | 0.035* | |
C13 | 0.6977 (6) | 0.0911 (3) | 0.35017 (11) | 0.0311 (6) | |
H13 | 0.8353 | 0.0214 | 0.3497 | 0.037* | |
C14 | 0.5957 (6) | 0.1557 (3) | 0.30589 (11) | 0.0252 (6) | |
C15 | 0.6936 (6) | 0.1211 (3) | 0.26118 (12) | 0.0302 (7) | |
H15 | 0.8344 | 0.0536 | 0.2598 | 0.036* | |
C16 | 0.5853 (6) | 0.1848 (3) | 0.21983 (11) | 0.0307 (6) | |
C17 | 0.3772 (6) | 0.2856 (3) | 0.22061 (11) | 0.0342 (7) | |
H17 | 0.3024 | 0.3276 | 0.1914 | 0.041* | |
C18 | 0.2840 (6) | 0.3222 (3) | 0.26353 (12) | 0.0337 (7) | |
H18 | 0.1456 | 0.3915 | 0.2641 | 0.040* | |
C19 | 0.3897 (5) | 0.2589 (3) | 0.30763 (10) | 0.0248 (6) | |
C20 | 0.2940 (5) | 0.2957 (3) | 0.35258 (11) | 0.0275 (6) | |
H20 | 0.1573 | 0.3656 | 0.3538 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0533 (3) | 0.0473 (3) | 0.0245 (2) | −0.01467 (14) | 0.01019 (15) | −0.00939 (13) |
O1 | 0.0420 (11) | 0.0227 (10) | 0.0276 (11) | 0.0120 (8) | 0.0127 (9) | 0.0034 (8) |
O2 | 0.0215 (11) | 0.0365 (11) | 0.0417 (13) | 0.0050 (8) | 0.0074 (9) | −0.0026 (10) |
O3 | 0.0249 (9) | 0.0192 (10) | 0.0301 (11) | 0.0044 (7) | 0.0067 (8) | 0.0016 (7) |
C1 | 0.0304 (14) | 0.0196 (13) | 0.0291 (16) | 0.0055 (10) | 0.0115 (12) | 0.0004 (11) |
C2 | 0.0255 (14) | 0.0241 (13) | 0.0143 (13) | 0.0055 (10) | 0.0030 (10) | 0.0011 (10) |
C3 | 0.0334 (15) | 0.0244 (14) | 0.0387 (18) | −0.0039 (11) | 0.0093 (13) | 0.0006 (13) |
C4 | 0.059 (2) | 0.0210 (15) | 0.058 (2) | 0.0044 (14) | 0.0215 (19) | 0.0020 (14) |
C11 | 0.0295 (13) | 0.0185 (12) | 0.0253 (15) | 0.0024 (10) | 0.0071 (11) | −0.0008 (11) |
C12 | 0.0351 (15) | 0.0256 (14) | 0.0280 (16) | 0.0111 (11) | 0.0059 (12) | 0.0043 (11) |
C13 | 0.0352 (15) | 0.0304 (15) | 0.0283 (16) | 0.0129 (12) | 0.0051 (12) | 0.0014 (13) |
C14 | 0.0295 (14) | 0.0205 (13) | 0.0256 (15) | −0.0016 (10) | 0.0031 (11) | −0.0039 (11) |
C15 | 0.0352 (15) | 0.0261 (15) | 0.0297 (16) | −0.0005 (11) | 0.0057 (13) | −0.0044 (12) |
C16 | 0.0373 (15) | 0.0307 (15) | 0.0246 (15) | −0.0110 (12) | 0.0058 (12) | −0.0053 (13) |
C17 | 0.0412 (16) | 0.0340 (16) | 0.0265 (16) | −0.0065 (13) | −0.0021 (13) | 0.0047 (13) |
C18 | 0.0365 (16) | 0.0328 (16) | 0.0316 (17) | 0.0061 (13) | 0.0012 (12) | 0.0032 (14) |
C19 | 0.0272 (13) | 0.0194 (13) | 0.0279 (15) | −0.0003 (10) | 0.0019 (11) | −0.0003 (11) |
C20 | 0.0291 (14) | 0.0227 (14) | 0.0312 (16) | 0.0089 (11) | 0.0056 (11) | 0.0021 (12) |
Br1—C16 | 1.907 (3) | C11—C12 | 1.421 (4) |
O1—C11 | 1.374 (3) | C12—C13 | 1.357 (4) |
O1—C1 | 1.428 (3) | C12—H12 | 0.9500 |
O2—C2 | 1.200 (3) | C13—C14 | 1.426 (4) |
O3—C2 | 1.330 (3) | C13—H13 | 0.9500 |
O3—C3 | 1.457 (3) | C14—C15 | 1.411 (4) |
C1—C2 | 1.513 (4) | C14—C19 | 1.417 (4) |
C1—H1A | 0.9900 | C15—C16 | 1.366 (4) |
C1—H1B | 0.9900 | C15—H15 | 0.9500 |
C3—C4 | 1.497 (4) | C16—C17 | 1.407 (5) |
C3—H3A | 0.9900 | C17—C18 | 1.360 (5) |
C3—H3B | 0.9900 | C17—H17 | 0.9500 |
C4—H4A | 0.9800 | C18—C19 | 1.423 (4) |
C4—H4B | 0.9800 | C18—H18 | 0.9500 |
C4—H4C | 0.9800 | C19—C20 | 1.417 (4) |
C11—C20 | 1.367 (4) | C20—H20 | 0.9500 |
C11—O1—C1 | 117.4 (2) | C13—C12—H12 | 120.0 |
C2—O3—C3 | 116.1 (2) | C11—C12—H12 | 120.0 |
O1—C1—C2 | 111.1 (2) | C12—C13—C14 | 121.5 (3) |
O1—C1—H1A | 109.4 | C12—C13—H13 | 119.2 |
C2—C1—H1A | 109.4 | C14—C13—H13 | 119.2 |
O1—C1—H1B | 109.4 | C15—C14—C19 | 119.6 (3) |
C2—C1—H1B | 109.4 | C15—C14—C13 | 122.4 (3) |
H1A—C1—H1B | 108.0 | C19—C14—C13 | 118.0 (3) |
O2—C2—O3 | 124.8 (3) | C16—C15—C14 | 119.8 (3) |
O2—C2—C1 | 125.5 (2) | C16—C15—H15 | 120.1 |
O3—C2—C1 | 109.7 (2) | C14—C15—H15 | 120.1 |
O3—C3—C4 | 106.8 (2) | C15—C16—C17 | 121.5 (3) |
O3—C3—H3A | 110.4 | C15—C16—Br1 | 119.8 (2) |
C4—C3—H3A | 110.4 | C17—C16—Br1 | 118.7 (2) |
O3—C3—H3B | 110.4 | C18—C17—C16 | 119.5 (3) |
C4—C3—H3B | 110.4 | C18—C17—H17 | 120.3 |
H3A—C3—H3B | 108.6 | C16—C17—H17 | 120.3 |
C3—C4—H4A | 109.5 | C17—C18—C19 | 121.3 (3) |
C3—C4—H4B | 109.5 | C17—C18—H18 | 119.4 |
H4A—C4—H4B | 109.5 | C19—C18—H18 | 119.4 |
C3—C4—H4C | 109.5 | C20—C19—C14 | 119.8 (3) |
H4A—C4—H4C | 109.5 | C20—C19—C18 | 121.9 (3) |
H4B—C4—H4C | 109.5 | C14—C19—C18 | 118.3 (3) |
C20—C11—O1 | 126.2 (2) | C11—C20—C19 | 120.3 (2) |
C20—C11—C12 | 120.4 (3) | C11—C20—H20 | 119.8 |
O1—C11—C12 | 113.4 (3) | C19—C20—H20 | 119.8 |
C13—C12—C11 | 120.0 (3) | ||
C11—O1—C1—C2 | −70.4 (3) | C14—C15—C16—C17 | 0.2 (4) |
C3—O3—C2—O2 | 2.1 (4) | C14—C15—C16—Br1 | −178.8 (2) |
C3—O3—C2—C1 | −178.9 (2) | C15—C16—C17—C18 | 1.0 (5) |
O1—C1—C2—O2 | −2.8 (4) | Br1—C16—C17—C18 | −179.9 (2) |
O1—C1—C2—O3 | 178.1 (2) | C16—C17—C18—C19 | −1.1 (5) |
C2—O3—C3—C4 | −178.7 (3) | C15—C14—C19—C20 | −178.9 (3) |
C1—O1—C11—C20 | −15.6 (4) | C13—C14—C19—C20 | 0.7 (4) |
C1—O1—C11—C12 | 165.1 (2) | C15—C14—C19—C18 | 1.3 (4) |
C20—C11—C12—C13 | 0.2 (5) | C13—C14—C19—C18 | −179.0 (3) |
O1—C11—C12—C13 | 179.5 (3) | C17—C18—C19—C20 | −179.8 (3) |
C11—C12—C13—C14 | −0.2 (5) | C17—C18—C19—C14 | −0.1 (4) |
C12—C13—C14—C15 | 179.3 (3) | O1—C11—C20—C19 | −179.0 (3) |
C12—C13—C14—C19 | −0.3 (4) | C12—C11—C20—C19 | 0.3 (4) |
C19—C14—C15—C16 | −1.4 (4) | C14—C19—C20—C11 | −0.7 (4) |
C13—C14—C15—C16 | 179.0 (3) | C18—C19—C20—C11 | 179.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O3i | 0.99 | 2.52 | 3.499 (3) | 169 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H13BrO3 |
Mr | 309.15 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 4.9979 (5), 9.3847 (7), 27.778 (3) |
β (°) | 94.857 (8) |
V (Å3) | 1298.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.16 |
Crystal size (mm) | 0.31 × 0.25 × 0.23 |
Data collection | |
Diffractometer | Stoe IPDSII two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.441, 0.530 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9302, 2376, 2076 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.604 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.103, 1.05 |
No. of reflections | 2376 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.86 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O3i | 0.99 | 2.52 | 3.499 (3) | 168.5 |
Symmetry code: (i) −x, −y+1, −z+1. |
The title compound is an intermediate in the preparation of naproxen, a non-steroidal anti-inflammatory drug (NSAID) commonly used for the reduction of high to extreme pain, fever, inflammation and stiffness caused by conditions such as osteoarthritis, rheumatoid arthritis, psoriatic arthritis, gout, ankylosing spondylitis, injury. Naproxen is a member of the 2-arylpropionic acid (profen) family of NSAIDs. The structures the related compounds viz., naproxen (Ravikumar et al., 1985), 6-methoxy-2-naphthyl acetic acid ester-glycolamide (Sharma et al., 2004), 1-(5-chloro-6-methoxynaphthalen-2-yl)propan-1-one (Ye et al., 2006), complex of a lisuride derivative and (S)-naproxen (Bachechi et al., 1997), absolute configuration of (R)-1-phenylethylammonium (S)-2-(6-methoxy-2-naphthyl)propionate (Dupont et al., 1996), N'-isopropylidene-6-methoxy-2-naphthohydrazide (Sarojini et al., 2007), ethyl 6-methoxy-2-naphthoate (Yathirajan et al., 2007) have been published. A new derivative was prepared and its crystal structure is reported.
Geometric parameters of the title compound are in the usual ranges. Neglecting the H atoms, the molecule comprises two planar halves, the bromonaphthyl moiety [r.m.s. deviation 0.010 Å] and the ethoxycarbonylmethoxy moiety [r.m.s. deviation 0.018 Å]. The dihedral angle between these moieties is 79.23 (7)°. The crystal packing is stabilized by a weak C—H···O hydrogen bond.